201144429 六、發明說明： 【發明所屬之技術頜域】 本發明涉及一種清洗劑組合物。 本申請要求2010年6月1日提交的韓國專利申請 10-2010-0055632的權益’通過援引將其全文併入本申請中。 【先前技術】 通常，在液晶單元的製造中，聚醯亞胺（PI)被塗在 兩個具有電極圖案的圖案化基板上以致被賦予取向層和絕 緣層的功能，且其上表面在預定的方向經受摩擦，從而形 成取向層。之後，用來控制液晶單元厚度的封口粘合劑和 隔離片被配置在基板之間’於是這兩片基板彼此結合在— 起。依此，如果污染物殘留在取向層基板上，在其上注入 液晶’很難獲得清晰的顯示幕’而且，包裝缺陷可能非期 差地產生。因此，需要用清洗工藝以從基板上除去污染物。 在製造液晶顯示器（LCDs)的液晶單元時，基板的污 朵物源可能包括在將兩片Π基板或pi粒子結合在一起前的 摩擦工蟄中使用的摩擦布中分離的雜質，且可能附著在基 板上，非期望地引起缺陷。在工藝中產生的這種污染物的 除去傳統上是用溶劑比如異丙醇或異丙醇水溶液，或純水 來完成的。但是，使用溶劑清洗是不利的，因為溶劑可能 殘留在基板的後面，且從對環境的安全性和包括易燃性的 =穩定性方面來說也可能是非期望地成問題的。此外， 隨著高油價時代的到來，使用溶劑清洗可能導致與原料價 ，增加成_的增加的王藝成本。而且，使祕水清洗也 沒顯示出充分的除去污染物的清洗能力，並因此相伴產生 生產產率的下隆。 3/19 201144429 此外，含驗性化合物的清洗财能非期望地損壞卿 向層。 還有’公職平3·620關日本專利公開了—種使用純 水進行摩擦基板的超聲清洗，,χ穩定地軸高的預傾角的 方法。但是，將超聲波引人製造顯示器的工藝中是不容易 的，且制純水清洗不能滿足近來所需的清^的性能。 公開號平3-8Π30的日本專利公開了—種使用刷子清洗摩捧 基板的表面的方法，但是由於產生來自刷子的二次污毕物 和污染物再次附著在基板上，所料可能期待理想的清洗 效果。 在上述曰本專利中，在清洗工藝中使用了施予物理的 清洗能力的設備，非期望地增加了清洗玉藝的成本，且也 不可避免齡㈣題，包括由於使用異鱗或者純水而使 溶劑殘留在基板上，沖洗不佳’粒子的再次附著等。 因此，為瞭解決以上提及的問題，在人體安全和工作 安全方面優越且通過外加各縣面活_能夠顯示高的清 洗能力和沖洗躲的各财性清洗线的研究在不斷進 行。 【發明内容】 口此本赉明曰在提供一種清洗劑組合物，其且 越的潤濕和料效果，由此從取向祕㈣上表面除去二 染物是非常有效的。 / 此外’本發明旨在提供一種不損壞取向層的清洗劑组 合物。 此外本t明曰在提供一種清洗劑組合物，其具有不 燃性’因此是安全的和對環境友好的，且具有低發泡性。 4/19 201144429 此外，本發明旨在提供一種清洗劑組合物，其不侵姓 包含鋼的金屬層和包含铭的金屬層。 本發明的一個方面提供一種不含鹼性化合物的清洗劑 組合物，其包含，基於組合物的總重，0.1〜15重量〜C5 的低級醇，0.1〜15重量％的水溶性乙二醇醚化合物，〇 〇1〜1〇 重量％的有機磷酸，〇·〇〇1〜10重量％的吡咯基化合物，和剩 餘物是水。 本發明的另一方面提供包含用上述清洗劑組合物清洗 的取向層的液晶單元。 本發明的更進一步的方面提供包含上述液晶單元的 LCD。 【實施方式】 在下文中給出本發明的詳細說明。 根據本發明的不含鹼性化合物的清洗劑組合物包含 C1〜C5低級醇，水溶性乙二醇_化合物’有機碟‘，=二 基化合物，和水。 逋常 蛻性亿兮物被用來除去來自空氣的污染物 機物質。但是，在鹼性化合物被用在製造LCDs的液晶二_ 過程中的情況下’可能損壞液晶取向層，特別是曰早7^ =因^根據本發明的清洗劑組合料含這樣的驗= σ物，從而阻止對液晶取向層的損壞。 此外，根據本發明的清洗劑組合物是有利的， C1〜C5低級醇，水溶性乙二醇醚化合物，和 為 合’從而在除去污染物和阻止取向層被損壞方結 ’和在製造顯示器的液晶單71過程中’麵棒^ 曰曰取向層之域讀清洗基板時，顯示出殘性和低發= 5/19 201144429 性。而且 ，該組合物在清洗液晶取向層特別 中對除去料物是非常有㈣，且，由於向層 根據本發明的清洗齡合物*猶包含& ‘ °物’ 含A1的金屬層，以致位於液晶取向層未被 ^ ^ 導線也不腐蝕。 I盈愿的電極或 根據本發明的清洗劑組合物中所含的c 增強了清洗劑對基板的·和㈣能力， =醇 染物=r能力，從而容易地從基板上除：物: 低，，及％可以按照基於組合物總重的01〜15 。使用’且優選G.5〜1G重量％。如果低級醇的量少於:重1 /〇’表面張力不降低，使其很難表現出潤濕和滲透能力。二 反’如果低級醇的量超過15重量％，低級醇可能合 板的後面，非期望地引起缺陷。 θ 土 C1〜C5低級醇的種類沒有特別限定，但是基於對包括 f溶性的特性的考慮，優選包括C1〜C4低級醇，例如，甲 醇上乙醇、正丙醇、異丙醇、乙二醇、1,2-丙二醇、ι,3_丙 醇 1，2 丁一醇、ι，3 丁一醇、ι,4_ 丁二醇、丙三醇、和 ι，2,4_ 丁一醇，可以單獨使用或者使用二種或以上的混合物。 在清洗劑組合物中所包含的水溶性乙二醇醚化合物在 除去油性組分和提高在水中的溶解性方面起作用，所述油 I"生組分被認為僅通過使用低級醇水溶液，很難從摩擦基板 的表面上除去。 水溶性乙二醇醚化合物可以按照基於組合物總重， 0.1〜15重量％的量使用，且優選〇 5〜〗〇重量％。如果水溶 性乙二醇醚化合物的量少於〇1重量％，很難從摩擦基板表 面除去油性組分。相反，如果水溶性乙二_化合物的量 6/19 201144429 超過二4量％，因此制得的清洗劑可能變得非常枯稠，從 而在/月洗工藝中其對基板的淵滿和摩透能力可能變差。 水溶性乙二醇醚化合物優選C1〜C10的水溶性乙二， 醚。Cl〜c_水雜乙二醇_例子可以包括乙二醇2 醚（MG)、二乙二醇單曱醚（MDG)、三乙二醇單甲喊 (MTG)/聚乙二醇單曱_(MpG)、乙二醇單乙呶邱）、 一乙一醇單乙醚（EDG)、乙二醇單丁醚（BG)、二乙_ 醇單丁醚（BDG)、三乙二醇單頂（BTG)、丙二醇^ 曱驗（MFG)、二丙二醇單_(MFDG)，其可以以獨 使用或者使用二種或以上的混合物。 根據本發明的清洗劑組合物中所含的有機磷酸起著分 散污染物粒子，使之不聚集的作用，而且在清洗工藝中^ 起提高對基板的潤濕和滲透能力的作用，進而改善;洗效 果。此外，有機磷酸可以有效地除去金屬粒子，並也可= 阻止包含Cu的金屬層和包含Ai的金屬層的腐蝕。 有機磷酸可以按照基於組合物總重，〇.〇1〜1〇重量％的 1使用’且優選0.1〜5重量％。如果有機磷酸的量低於〇 〇1 重1%，對被摩擦的基板的表面的潤濕和滲透能力不能增 加。相反，如果有機磷酸的量超過】〇重量％，這個組分可 能殘存在基板的後面，非期望地引起缺陷。 有機磷酸的例子沒有特別限定，包括氨基三亞曱基膦 酸、亞乙基二膦酸、卜羥基亞乙基'^二膦酸、卜羥基亞丙 基-U-二膦酸、1-羥基亞丁基·u_二膦酸、乙基氨基二亞曱 基膦酸、1,2-丙二胺四亞曱基膦酸、十二烷基氨基二亞曱基 膦酸、硝基三亞曱基膦酸（nitrotris(methyleneph〇sph〇nic acid))、乙二胺二亞曱基膦酸、乙二胺四亞曱基膦酸、己烯 7/19 201144429 二胺四亞甲基膦酸、二乙三胺五亞甲基膦酸、環己二胺四 亞曱基膦酸、羥基磷醯乙酸及2-膦酸-丁烷-1,2,4-三羧酸。 特別有用的是1-羥基亞乙基-U-二膦酸、羥基磷醯乙酸、 氨基三亞甲基膦酸或2-膦酸-丁烷-1,2,4-三羧酸。 根據本發明的清洗劑組合物中所含的°比σ各基化合物將 包含Cu的金屬層和包含Α1的金屬層的腐姓減至最低。 吡咯基化合物可以按照基於組合物總重，0.001〜10重 量％的量使用，及優選0.01〜3重量％。當該組分的用量落 入上述範圍内時，對包含Cu的金屬層和包含A1的金屬層 的損壞，也就是，其腐蝕可以被減至最低，且可以產生經 濟效益。 優選以下面的分子式1代表的吡咯基化合物。 分子式1201144429 VI. Description of the Invention: [Technological Jaw Domain to Which the Invention Is Applicable] The present invention relates to a cleaning composition. The present application claims the benefit of Korean Patent Application No. 10-2010-0055632, filed on Jun. [Prior Art] Generally, in the manufacture of a liquid crystal cell, polyimine (PI) is coated on two patterned substrates having an electrode pattern so as to be imparted with an orientation layer and an insulating layer, and the upper surface thereof is predetermined The direction is subjected to friction to form an alignment layer. Thereafter, a sealing adhesive and a separator for controlling the thickness of the liquid crystal cell are disposed between the substrates, and then the two substrates are bonded to each other. Accordingly, if contaminants remain on the alignment layer substrate, it is difficult to obtain a clear display screen by injecting liquid crystal thereon, and packaging defects may be generated in an unprobable manner. Therefore, a cleaning process is required to remove contaminants from the substrate. When manufacturing liquid crystal cells of liquid crystal displays (LCDs), the source of the substrate may include impurities separated in a rubbing cloth used in a rubbing process before bonding two pieces of tantalum substrates or pi particles together, and may adhere On the substrate, defects are undesirably caused. The removal of such contaminants produced in the process is conventionally accomplished with a solvent such as an aqueous solution of isopropanol or isopropanol, or pure water. However, the use of solvent cleaning is disadvantageous because the solvent may remain behind the substrate and may also be undesirably problematic in terms of environmental safety and stability including flammability. In addition, with the advent of the era of high oil prices, the use of solvent cleaning may result in an increase in the price of raw materials, increasing the cost of Wang Yi. Moreover, the cleaning of the secret water did not show sufficient cleaning ability to remove contaminants, and thus accompanied by a production yield. 3/19 201144429 In addition, cleaning supplies containing test compounds undesirably damage the layer. There is also a method of using a pure water for ultrasonic cleaning of a friction substrate, and a stable pre-tilt angle of the shaft height, as disclosed in Japanese Patent No. 3,620. However, it is not easy to introduce ultrasonic waves into the manufacturing process of the display, and the pure water cleaning cannot satisfy the performance required recently. Japanese Patent Publication No. Hei 3-8Π30 discloses a method of cleaning a surface of a substrate using a brush, but since secondary stains and contaminants from the brush are reattached to the substrate, it may be desirable to expect. Cleaning effect. In the above-mentioned Japanese patent, the use of equipment for applying physical cleaning ability in the cleaning process undesirably increases the cost of cleaning jade, and is also inevitable (4), including the use of different scales or pure water. The solvent is left on the substrate, and the rinsing is poor, and the particles are reattached. Therefore, in order to solve the above-mentioned problems, research on superior human safety and work safety, and through the addition of various county-level activities, which can show high cleaning ability and flushing, have been continuously conducted. SUMMARY OF THE INVENTION The present invention provides a cleaning composition which is more effective in removing the dye from the upper surface of the orientation (4). Further, the present invention is intended to provide a cleaning composition which does not damage the orientation layer. Further, the present invention provides a cleaning composition which is incombustible & is therefore safe and environmentally friendly, and has low foaming properties. 4/19 201144429 Furthermore, the present invention is directed to a cleaning composition which does not infringe the metal layer comprising steel and the metal layer comprising the inscription. One aspect of the present invention provides a cleaning composition containing no basic compound, comprising 0.1 to 15% by weight of a lower alcohol, 0.1 to 15% by weight of a water-soluble glycol ether based on the total weight of the composition. The compound, 〇〇1 to 1% by weight of the organic phosphoric acid, 〇·〇〇1 to 10% by weight of the pyrrolyl compound, and the remainder is water. Another aspect of the invention provides a liquid crystal cell comprising an alignment layer cleaned with the above cleaning agent composition. A still further aspect of the invention provides an LCD comprising the above liquid crystal cell. [Embodiment] A detailed description of the present invention is given below. The detergent composition containing no basic compound according to the present invention comprises a C1 to C5 lower alcohol, a water-soluble ethylene glycol-compound 'organo disc', a dibasic compound, and water.逋 蜕 蜕 兮 兮 被 被 is used to remove pollutants from the air. However, in the case where a basic compound is used in the process of manufacturing a liquid crystal of LCDs, the liquid crystal alignment layer may be damaged, in particular, the cleaning composition according to the present invention contains such a test = σ Object, thereby preventing damage to the liquid crystal alignment layer. Further, the cleaning composition according to the present invention is advantageous in that a C1 to C5 lower alcohol, a water-soluble glycol ether compound, and a combination are formed so that the contaminant is removed and the alignment layer is prevented from being damaged, and the display is manufactured. During the process of liquid crystal single 71, the surface of the 面 ^ 曰曰 曰曰 曰曰 读 读 读 读 读 读 读 读 读 读 读 读 读 读 读 读 读 读 读 读 读 读 读 读Moreover, the composition is particularly useful for removing the material in the cleaning of the liquid crystal alignment layer, and since the cleaning layer according to the present invention is contained in the layer, the metal layer containing A1 is included. The liquid crystal alignment layer is not etched by the ^^ wire. The electrode of the I wish or the c contained in the cleaning composition according to the present invention enhances the ability of the cleaning agent to the substrate and/or the ability of the alcohol dye = r to easily remove from the substrate: , and % can be based on the total weight of the composition of 01~15. Use 'and preferably G.5 to 1 G% by weight. If the amount of lower alcohol is less than: weight 1 / 〇 ' surface tension is not lowered, making it difficult to exhibit wetting and penetration ability. If the amount of the lower alcohol exceeds 15% by weight, the lower alcohol may be behind the laminate, undesirably causing defects. The type of the C1 to C5 lower alcohol of the θ soil is not particularly limited. However, it is preferable to include a C1 to C4 lower alcohol, for example, ethanol, n-propanol, isopropanol or ethylene glycol, based on the characteristics of the solubility of f. 1,2-propanediol, iota, 3-propanol 1,2 butanol, iota, butanol, iota, 4-butanediol, glycerol, and iota, 2,4-butanol, can be used alone Alternatively, a mixture of two or more may be used. The water-soluble glycol ether compound contained in the detergent composition plays a role in removing the oil component and improving the solubility in water, and the oil I" raw component is considered to be only by using a lower alcohol aqueous solution, It is difficult to remove from the surface of the friction substrate. The water-soluble glycol ether compound can be used in an amount of 0.1 to 15% by weight based on the total weight of the composition, and preferably 〇 5 to 〇 〇 by weight. If the amount of the water-soluble glycol ether compound is less than 〇1% by weight, it is difficult to remove the oil component from the surface of the friction substrate. On the contrary, if the amount of the water-soluble ethylene compound is 6/19 201144429 more than 2-4%, the resulting cleaning agent may become very thick, so that it is full and perfect for the substrate in the /month washing process. Ability may be worse. The water-soluble glycol ether compound is preferably a water-soluble ethylene glycol or an ether of C1 to C10. Cl~c_hydroethylene glycol_examples may include ethylene glycol 2 ether (MG), diethylene glycol monoterpene ether (MDG), triethylene glycol monomethyl shunt (MTG) / polyethylene glycol monoterpene _(MpG), ethylene glycol monoethyl oxime), monoethyl alcohol monoethyl ether (EDG), ethylene glycol monobutyl ether (BG), diethyl ether monobutyl ether (BDG), triethylene glycol single top (BTG), propylene glycol (MFG), dipropylene glycol mono- (MFDG), which may be used alone or in a mixture of two or more. The organic phosphoric acid contained in the cleaning agent composition according to the present invention functions to disperse the contaminant particles so as not to aggregate, and to improve the wetting and permeating ability of the substrate in the cleaning process, thereby improving; Wash the effect. Further, the organic phosphoric acid can effectively remove the metal particles, and can also prevent corrosion of the metal layer containing Cu and the metal layer containing Ai. The organic phosphoric acid may be used in an amount of -1 and preferably 0.1 to 5% by weight based on 1% by weight based on the total weight of the composition. If the amount of the organic phosphoric acid is less than 1% by weight of 〇1, the wetting and penetration ability to the surface of the substrate to be rubbed cannot be increased. On the contrary, if the amount of the organic phosphoric acid exceeds 5% by weight, this component may remain behind the substrate, undesirably causing defects. Examples of the organic phosphoric acid are not particularly limited, and include aminotrikisylphosphonic acid, ethylenediphosphonic acid, hydroxyethylidene'diphosphonic acid, hydroxypropylidene-U-diphosphonic acid, and 1-hydroxybutyric acid. ·u_diphosphonic acid, ethylaminodipyridylphosphonic acid, 1,2-propanediaminetetradecylphosphonic acid, dodecylaminodipyridylphosphonic acid, nitrotriphosphonium phosphine Acid (nitrotris(methyleneph〇sph〇nic acid)), ethylenediamine dipyridinylphosphonic acid, ethylenediaminetetradecylphosphonic acid, hexene 7/19 201144429 diamine tetramethylene phosphonic acid, diethyl Triamine penta methylene phosphonic acid, cyclohexanediamine tetradecylphosphonic acid, hydroxyphosphonium acetic acid and 2-phosphonic acid-butane-1,2,4-tricarboxylic acid. Particularly useful are 1-hydroxyethylidene-U-diphosphonic acid, hydroxyphosphonium acetic acid, aminotrimethylenephosphonic acid or 2-phosphonic acid-butane-1,2,4-tricarboxylic acid. The ratio of σ-based compounds contained in the cleaning composition according to the present invention minimizes the rot of the metal layer containing Cu and the metal layer containing Α1. The pyrrolyl compound can be used in an amount of 0.001 to 10% by weight based on the total weight of the composition, and preferably 0.01 to 3% by weight. When the amount of the component falls within the above range, the damage to the metal layer containing Cu and the metal layer containing A1, that is, the corrosion thereof can be minimized, and economic benefits can be obtained. A pyrrolyl compound represented by the following Formula 1 is preferred. Molecular formula 1
在分子式1中，R|，尺2和尺3是各自獨立的氫原子、鹵 素原子、C1〜C6烷基、C3〜C6環烷基、烯丙基、芳基、氨 基、C1〜C6 :)：完氨基、硝基、氰基、魏基(mercapto group)、 Cl〜C6烷巯基、羥基、Cl〜C6羥烷基、羧基、Cl〜C6羧烷 基、醯基、C1〜C6烷氧基、或者雜環的單價的基團。 由分子式1所代表的吡咯基化合物可以選自由N-[(苯 並三唑）曱基]二乙醇胺、N-[(曱基-1H-苯並三唑-1-基）曱基] 二甲醇胺、N-[(乙基-1H-苯並三唑-1-基）甲基]二乙醇胺、 N-[(曱基-1H-苯並三唑-1-基）曱基]二丙醇胺、2,2’-[[(曱基 8/19 201144429 jH_苯並H基)甲基]亞氨基]:賴、2,2，_[[(甲基-1H-本亚一坐，1-基）甲基]亞氨基]二曱胺、和N_[(胺_瓜苯並三唾 _1_基）甲基]二乙醇胺組成的組。 一 此外，根據本發明的清洗劑組合物中所包含的水μ有 特別限定’但是可吨括適合於半導體玉藝的去離子^， 且具^至少18ΜΩ,的電阻率。水的量可以根據其他的組 分的量進行調整。基於組合物總重，加人水作為剩餘物， 以使組合物的總的重量百分數為1〇〇。 、 根據本發明的清洗劑組合物中不含有機酸是優選的。 理由是當含有機酸的清洗劑組合物在LCDs製造中在摩擦 取向層後使用時，金屬粒子可以被有效地從取向層，特別 是PI取向層的表面除去，但是’金屬電極或導線的腐钱也 可能被加速。 為了提高清洗性能，根據本發明的清洗劑組合物可以 進一步包含本領域已知的通常的添加劑，例如，防蝕劑、 潤濕/滲透劑、分散劑、表面改性劑等。 根據本發明的清洗劑組合物的組分可以使用通常已知 的方法製備，且優選具有適合半導體工藝的純度。 此外，本發明提供包含使用上述清洗劑組合物清洗的 取向層較晶單元，另外’本發明提供包含上述液晶 的 LCD。 當使用根據本發明的清洗劑組合物時，在取向層基板 上的3染物餘潰能被完全除去’由此包含這樣的取向層的 液晶單元具有高的品質。而^，包含這#的液晶單元的 能夠提供清晰的顯示幕幕。 使用根據本發明的清洗劑組合物的清洗方法，沒有特 9/19 201144429 啊ying)、、以包括浸泡、祕、超聲降解、喷灑(shower 幻搗漿(puddling)、刷等。 果，發明的清洗胁合*具有優越的潤濕和滲透效 去。访J?在於取向層基板上的污染物能夠被有效地除 南展IB發明的清洗劑組合物不損壞包括在1(：〇中的取 晶二於在製造LCD的液晶單元過程中，在摩擦液 L Β θ別或之後的清洗基板是料有效的。特別是， 當該清洗劑組合物被應用在製造LCD工藝中時，金屬粒子 能夠被有效地從取向層的上表面除去。而且，根據本發明 的清洗劑組合物是不燃的，由此是安全和對環境友好的且 不會引起起泡問題。根據本發明的清洗劑組合物也不腐蝕 包含Cu的金屬層和包含A1的金屬層。 ' 通過下述實例可以獲得對本發明更好的理解，這此电 例是用來詳盡說明’而不是被解釋為限制本發明的。一貝 實例1〜11和對比實例1〜8 :清洗劑組合物的製備 將下表1中顯示的組分以預定的量添加到一個裳 攪拌器的混合容器中，在室溫下以500rpm的速度攪^夏 時’從而製備出清洗劑組合物。 小 10/19 201144429 表1 驗性化合物 級醇 乙二醇醚 有機磷酸 0比略基化合物 有機酸 去離子水 序號 種 數量 數量 數量 類 (\vt%) 種類 數量(Wt%) 種類 數量（\vt%) 種類 數量（Wt%> 種類 數量（wt%) 種類 (wt%) (wt%) 1 - - A-1 5 B-] 5 C-l 1 D-l 0.2 - - 餘量 2 - - A-1 5 B-1 5 C-l 1 D-2 0.2 - - 餘量 3 - - Α·1 5 B-l 5 C-2 1 D-l 0.2 - - 餘量 4 - - A-1 5 B-l 5 C-3 1 D-l 0.2 - - 餘量 5 - - A-1 5 Β·2 5 C-l 1 D-l 0.2 - - 餘量 6 - - A-1 5 B-3 5 C-l 1 D-l 0.2 - - 餘量 7 - - A-2 5 B-2 5 C-l 1 D-l 0.2 - - 餘量 8 - - A-3 5 B-2 5 C-l 1 D-l 0.2 - - 餘量 9 - - A-2 5 B-2 5 C-l 2 D-l 0.5 - - 餘量 10 - A-2 5 B-2 10 C-l 2 D-l 0.5 - - 餘量 11 A-2 10 B-l 5 C-l 2 D-l 0.5 琴 - 餘量 C.1 ΤΜΑΗ 0.4 - - - * - - - - - - 99.6% C.2 - - A-2 30 - - - - - - - - 餘量 C.3 - - - - B-2 20 - - - - - - 餘量 C.4 - - - - - - C-2 2 - - - - 餘量 C.5 ΤΜΑΗ 0.4 A-1 5 B-l 5 C-l 0.5 D-l 0.5 * - 餘量 C.6 - - A-2 5 B-2 5 C-l 2 • • • • 余量 C.7 - - - - - - - • . • 100% C.8 - A-1 5 B-l 5 - - D-l 0.2 E-1 2 余量 A-l:乙醇 A-2:異丙醇 A-3:丙三醉 B-1:二乙二醇單曱醚（MDG) B-2:二乙二醇單乙醚（EDG) B-3:二乙二醇單丁醚（BDG) C-l: 1-羥基亞乙基-1,1-二膦酸(HEDP) C-2: 2-膦酸-丁烷-1，2,4-三羧酸(PBTC) C-3:羥基磷醯乙酸(ΗΡΑ) D-l: Ν-[(乙基-1Η-苯並三基）曱基]二乙醇胺 D-2: Ν-[(胺-1Η-苯並三喷-l-基）曱基]二乙醇胺 11/19 201144429 TMAH:四甲基氫氧化銨 E-1:乙二酸 試驗實例：清洗能力和對取向層的損壞的評估 L對pi取向層的損壞和除去粒子能力的評估 個基板（5_5咖>:〇.7他），其}>1取向層已經被摩 二使其處於空氣中24小時，以致它被各種有機物、無機 ^粒子等H紐使时_㈣朗絲清洗裝置， 用=例1〜11和對比實例j，每—種清洗劑組合物在室溫 ^洗2刀！里。清洗後’用超純水沖洗基板秒並用氮氣 乾燥i用掃描電子顯微鏡（SEM) (s_47〇〇，由曰立公司提 供）觀察由此獲得的基板，來評價ρι取向層是否被損壞並 根據殘留在基板後面的雜質粒子的數目來評價清洗能力。 θ結果顯示在下表2中，其中◎是優越，〇是良好，△ 疋中等，及X疋差的。當ΡΙ取向層被剝離時，不能測量 出結果，這種情況用表示。 2.除去有機污染物能力的評估 一個玻璃基板，使其處在空氣中24小時，以致其被各 種有機物、無機物、粒子等污染，之後向其滴加〇5μ丨的超 純水’在清洗之前測量接觸角以確認表面污染。具體地， 將只例1〜11和對比實例1〜8的每一種清洗劑組合物！ 加入到一個250ml燒杯中，在室溫下將玻璃基板浸泡其中2 分鐘並清洗。之後’用超純水沖洗基板30秒並用氮氣乾燥。 將〇.5μ1的超純水滴加到玻璃基板上測量清洗後的接觸角。 結果顯示在下表2中’其中當清洗後接觸角的變化是 30°或更大時判定為◎，接觸角的變化從15。到少於3〇。時 12/19 201144429 判定為〇，接觸角的變化從5。到少於15。時判定為厶， 接觸角的變化是5。或者更小時判定為X。 ’' 及 3. 對Al、Cu的損壞的評估 為評估對導線的損壞，使用Mo/Al/Mo佈線基板評估對 A1的損壞，及使用Cu/Ti佈線基板評料&的損壞。具體 地，將實例卜11和對比實例丨〜8的每—種清洗劑組合物 l〇〇ml加入到250ml燒杯中，且在室溫下（25。）將玻璃基 板浸泡其中30分鐘並清洗。之後，用超純水沖洗基板3〇 秒並用氮氣乾燥。用SEM (S_4700,由日立公司提供）觀 察基板的A1和Cu是否被損壞。結果顯示在下表2中。 對導線的損壞的評估結果也顯示在圖1至4中。In Formula 1, R|, Size 2 and Rule 3 are independent hydrogen atoms, halogen atoms, C1 to C6 alkyl groups, C3 to C6 cycloalkyl groups, allyl groups, aryl groups, amino groups, C1 to C6 :) : amino, nitro, cyano, mercapto group, Cl~C6 alkyl fluorenyl, hydroxy, Cl~C6 hydroxyalkyl, carboxyl, Cl~C6 carboxyalkyl, fluorenyl, C1~C6 alkoxy Or a monovalent group of a heterocyclic ring. The pyrrolyl compound represented by the formula 1 may be selected from N-[(benzotriazol)indolyl]diethanolamine, N-[(indolyl-1H-benzotriazol-1-yl)indenyl]dimethanol Amine, N-[(ethyl-1H-benzotriazol-1-yl)methyl]diethanolamine, N-[(indolyl-1H-benzotriazol-1-yl)indolyl]dipropanol Amine, 2,2'-[[(indolyl 8/19 201144429 jH_benzoh-yl)methyl]imino]: La, 2,2, _[[(methyl-1H-Benya sits, a group consisting of 1-yl)methyl]imino]diamine, and N_[(amine-guar benzotrisyl)methyl]diethanolamine. Further, the water μ contained in the detergent composition according to the present invention is particularly limited 'but can be deionized to be suitable for semiconductor jade, and has a resistivity of at least 18 Ω. The amount of water can be adjusted according to the amount of other components. Based on the total weight of the composition, human water was added as a residue so that the total weight percentage of the composition was 1 Torr. It is preferred that the cleaning agent composition according to the invention does not contain an organic acid. The reason is that when the cleaning agent composition containing organic acid is used after rubbing the alignment layer in the manufacture of LCDs, the metal particles can be effectively removed from the surface of the alignment layer, particularly the PI alignment layer, but the corrosion of the metal electrode or the wire Money may also be accelerated. In order to improve the cleaning performance, the cleaning composition according to the present invention may further contain usual additives known in the art, for example, an anti-corrosion agent, a wetting/penetrating agent, a dispersing agent, a surface modifying agent and the like. The components of the cleaning composition according to the present invention can be produced by a generally known method, and preferably have a purity suitable for a semiconductor process. Further, the present invention provides an alignment layer containing crystal unit which is cleaned by using the above cleaning agent composition, and the present invention provides an LCD comprising the above liquid crystal. When the cleaning composition according to the present invention is used, the 3 dye residue on the alignment layer substrate can be completely removed. Thus, the liquid crystal cell containing such an alignment layer has high quality. And ^, the liquid crystal unit containing this # can provide a clear display screen. The cleaning method using the cleaning agent composition according to the present invention, without special 9/19 201144429, to include soaking, secret, ultrasonic degradation, spraying (shower phantom pudding, brush, etc.), invention The cleaning threat* has superior wetting and osmosis effect. Interview J: The contaminant on the oriented layer substrate can be effectively removed except for the cleaning agent composition of the invention of Nanzhan IB. It is effective to clean the substrate in or after the friction liquid L Β θ during the manufacture of the liquid crystal cell of the LCD. In particular, when the cleaning composition is applied in the manufacture of an LCD process, the metal particles are used. It can be effectively removed from the upper surface of the alignment layer. Moreover, the cleaning composition according to the present invention is non-combustible, thereby being safe and environmentally friendly and does not cause foaming problems. The cleaning agent combination according to the present invention The material also does not corrode the metal layer containing Cu and the metal layer containing A1. A better understanding of the present invention can be obtained by the following examples, which are intended to be exhaustive and not to be construed as limiting the invention. One Shell Examples 1 to 11 and Comparative Examples 1 to 8: Preparation of Detergent Composition The components shown in Table 1 below were added in a predetermined amount to a mixing vessel of a skirt mixer at 500 rpm at room temperature. The speed is stirred in the summer time to prepare a cleaning agent composition. Small 10/19 201144429 Table 1 Qualitative compound grade alcohol glycol ether organic phosphoric acid 0 ratio thiol compound organic acid deionized water serial number quantity quantity class (\ Vt%) Species quantity (Wt%) Species quantity (\vt%) Species quantity (Wt%> Species quantity (wt%) Species (wt%) (wt%) 1 - - A-1 5 B-] 5 Cl 1 Dl 0.2 - - Balance 2 - - A-1 5 B-1 5 Cl 1 D-2 0.2 - - Balance 3 - - Α·1 5 Bl 5 C-2 1 Dl 0.2 - - Balance 4 - - A-1 5 Bl 5 C-3 1 Dl 0.2 - - Balance 5 - - A-1 5 Β·2 5 Cl 1 Dl 0.2 - - Balance 6 - - A-1 5 B-3 5 Cl 1 Dl 0.2 - - Balance 7 - - A-2 5 B-2 5 Cl 1 Dl 0.2 - - Balance 8 - - A-3 5 B-2 5 Cl 1 Dl 0.2 - - Balance 9 - - A-2 5 B -2 5 Cl 2 Dl 0.5 - - balance 10 - A-2 5 B-2 10 Cl 2 Dl 0.5 - - balance 11 A-2 10 Bl 5 Cl 2 Dl 0.5 Piano - Balance C.1 ΤΜΑΗ 0.4 - - - * - - - - - - 99.6% C.2 - - A-2 30 - - - - - - - - Balance C.3 - - - - B-2 20 - - - - - - Balance C.4 - - - - - - C-2 2 - - - - Balance C.5 ΤΜΑΗ 0.4 A-1 5 Bl 5 Cl 0.5 Dl 0.5 * - Balance C.6 - - A-2 5 B-2 5 Cl 2 • • • • Balance C.7 - - - - - - - • • • 100% C.8 - A-1 5 Bl 5 - - Dl 0.2 E-1 2 balance Al: ethanol A-2: isopropanol A-3: propylene trihydrate B-1: diethylene glycol monoterpene ether (MDG) B-2: diethylene glycol monoethyl ether (EDG) B-3 Diethylene glycol monobutyl ether (BDG) Cl: 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) C-2: 2-phosphonic acid-butane-1,2,4-tricarboxylate Acid (PBTC) C-3: hydroxyphosphonium acetic acid (ΗΡΑ) Dl: Ν-[(ethyl-1 Η-benzotriyl) fluorenyl] diethanolamine D-2: Ν-[(amine-1Η-benzo) Tris-l-yl) fluorenyl] diethanolamine 11/19 201144429 TMAH: tetramethylammonium hydroxide E-1: oxalic acid Test example: cleaning ability and evaluation of damage to the alignment layer L on the pi orientation layer Evaluation of damage and particle removal ability of the substrate (5_5 coffee >: 〇.7 he), its } 1 orientation layer has been immersed in the air 24 Hours, so that it is used by various organic substances, inorganic particles, etc. _ (four) Langsi cleaning device, with = 1 to 11 and comparative example j, each cleaning agent composition at room temperature ^ 2 knives! in. After washing, the substrate was washed with ultrapure water for a second and dried with nitrogen. The substrate thus obtained was observed by a scanning electron microscope (SEM) (s_47〇〇, supplied by Philippine Co., Ltd.) to evaluate whether the pH layer was damaged or not. The cleaning ability was evaluated by the number of impurity particles behind the substrate. The results of θ are shown in Table 2 below, where ◎ is superior, 〇 is good, Δ 疋 is medium, and X 疋 is poor. When the tantalum orientation layer is peeled off, the result cannot be measured, and this case is indicated. 2. Evaluation of the ability to remove organic pollutants A glass substrate was allowed to stand in the air for 24 hours, so that it was contaminated with various organic substances, inorganic substances, particles, etc., and then 〇5 μ丨 of ultrapure water was added thereto. The contact angle was measured to confirm surface contamination. Specifically, only each of the cleaning compositions of Examples 1 to 11 and Comparative Examples 1 to 8 will be used! Add to a 250 ml beaker, soak the glass substrate for 2 minutes at room temperature and wash. Thereafter, the substrate was rinsed with ultrapure water for 30 seconds and dried with nitrogen. An ultrapure water drop of 〇5 μl was applied to the glass substrate to measure the contact angle after washing. The results are shown in Table 2 below, where it was judged as ◎ when the change in contact angle after washing was 30 or more, and the change in contact angle was from 15. It is less than 3 〇. When 12/19 201144429 was judged as 〇, the contact angle changed from 5. To less than 15. When the time is judged to be 厶, the change in the contact angle is 5. Or judge X as being smaller. ’' and 3. Evaluation of damage to Al and Cu In order to evaluate the damage to the wires, the damage to A1 was evaluated using a Mo/Al/Mo wiring substrate, and the damage of the Cu/Ti wiring substrate was evaluated. Specifically, each of the detergent compositions of Example 11 and Comparative Example 丨 8 was added to a 250 ml beaker, and the glass substrate was immersed therein for 30 minutes at room temperature (25 °) and washed. Thereafter, the substrate was rinsed with ultrapure water for 3 sec and dried with nitrogen. The SEM (S_4700, supplied by Hitachi, Ltd.) was used to observe whether the substrates A1 and Cu were damaged. The results are shown in Table 2 below. The evaluation results of the damage of the wires are also shown in Figs.
正如從表2可見的，根據本發明的實例丨〜丨丨的所有清 洗劑組合物顯示了優越的清洗能力且沒有引起對PI取向層 13/19 201144429 的損壞。而且，沒有觀察到對 然而，對比實例J中含少D U的損壞。 物完全除去了 PI取向層並損壞；化合物的清洗劑組告 而且對比實例2的、、主唑淑丨知人t匕3 AI和Cu的金屬a， 卻引起有機材料殘的口後勿^除去雜質是有效的， 地產生缺陷。對比實例3 形成汗物，非期望 層的損壞，但是具有低的除去;起對取向 =:組=有_取向層二 組合物非期望地損壞了 Cu。僅麵水崎比實例7的清^ 劑組合物料起對PI取向層的損壞但是義望地顯示出低 =2含有機酸的對比實例8清洗劑組合物非期 同時，圖1疋顯示使用貫例1的清洗劑組合物清洗 Cu/Ti佈線基板時cu表面的圖片，圖2是顯示使用實例2 的清洗劑組合物清洗Mo/Al/Mo佈線基板時A1表面的照 片’圖3是顯示使用對比實例1的清洗劑組合物清洗 Mo/Ai/Mo-佈線基板時A1表面的照片，圖4是顯示使用對 比實例1的清洗劑組合物清洗Cu/Ti佈線基板時Cu表面的 照片。 關於圖1至4，根據本發明的實例1和2的清洗劑組 合物沒有引起對Cu/Ti導線和Mo/Al/Mo導線的損壞。但 是，對比實例1的清洗劑組合物損壞了 Cu/Ti導線和 Mo/Al/Mo導線的全部。 14/19 201144429 如上文中所描述的，本 透效果的清洗劑組合物且在了具有優秀潤濕和滲 物方面是非常有效的。根層基板上表面除去污染 包括在LCD中的取⑽，且因:的清洗劑組合物不損壞 沾该曰。一a 曰且因此能夠顯示出在製造lxDsAs can be seen from Table 2, all of the detergent compositions according to the examples of the present invention showed superior cleaning ability and did not cause damage to the PI alignment layer 13/19 201144429. Moreover, no observation was made. However, in Comparative Example J, damage with less D U was contained. The material completely removed the PI alignment layer and was damaged; the cleaning agent of the compound was compared with the metal a of Comparative Example 2, the main azole, the 匕3 AI and the Cu, but the organic material remained after the mouth was removed. It is effective and the ground is defective. Comparative Example 3 formed sweat, undesired layer damage, but with low removal; pairwise orientation =: group = with - orientation layer 2 The composition undesirably damaged Cu. The surface water-repellent combination material of Example 7 only damaged the PI alignment layer but was expected to show a low = 2 containing the organic acid. The comparative example 8 cleaning agent composition was not in the same period, and FIG. A picture of the surface of cu when the cleaning composition of 1 is cleaned of the Cu/Ti wiring substrate, and FIG. 2 is a photograph showing the surface of A1 when the Mo/Al/Mo wiring substrate is cleaned using the cleaning composition of Example 2, FIG. 3 is a comparison of use. A photograph of the surface of A1 when the cleaning composition of Example 1 was washed with a Mo/Ai/Mo-wiring substrate, and FIG. 4 is a photograph showing the surface of Cu when the Cu/Ti wiring substrate was cleaned using the cleaning composition of Comparative Example 1. With respect to Figures 1 to 4, the cleaning composition of Examples 1 and 2 according to the present invention did not cause damage to the Cu/Ti wire and the Mo/Al/Mo wire. However, the cleaning composition of Comparative Example 1 damaged all of the Cu/Ti wire and the Mo/Al/Mo wire. 14/19 201144429 As described above, the permeable cleaning composition is very effective in having excellent wetting and bleeding. The top surface of the root substrate is decontaminated and included in the LCD (10), and the cleaning agent composition does not damage the crucible. a 曰 and therefore can show the manufacture of lxDs
Wa早7L雜巾在摩驗日日日 f洗方面的優越的效果。特別是，二^ =^物=㈣造LCD時’其除去位於取向層上的金屬 的疋而的。根據本發明的清洗劑組合物是不辦 Γ二rf全和對環境友好的，且不產生氣泡問題。而 據本發明的清洗劑組合物不腐茲包含Cu的金屬層和 包含Α1的金屬層。 儘管本發明的優選的實施方式為了說明的目的已經被 Α開了’但疋本領域技術人員會知曉不需脫離從附隨的權 利要求中公開的發明的範圍和主旨，進行各種修改、增加、 和替代是可能的。 【圖式簡單說明】 由結合相應附圖的以下詳細說明將更清楚地理解本發 明的特徵和優點，其中： 圖1顯不了當使用實例丨的清洗劑組合物清洗Cu/Ti佈線 基板時Cu的表面； 圖2顯示了當使用實例2的清洗劑組合物清洗m〇/a1/m〇 佈線基板時A1的表面； 圖3顯示了當使用比較例丨的清洗劑組合物清洗 Mo/Al/Mo佈線基板時A1的表面；和 圖4顯示了當使用比較例1的清洗劑組合物清洗㈤^佈 線基板時Cu的表面。 15/19 201144429 【主要元件符號說明】 無 16/19Wa early 7L miscellaneous towel in the day of the test day f wash the superior effect. In particular, when the LCD is made, it removes the defects of the metal on the alignment layer. The cleaning composition according to the present invention is not environmentally friendly and does not cause bubble problems. Further, the cleaning composition according to the present invention does not contain a metal layer of Cu and a metal layer containing ruthenium 1. Although the preferred embodiment of the present invention has been described herein for the purpose of illustration, it will be understood by those skilled in the art And alternatives are possible. BRIEF DESCRIPTION OF THE DRAWINGS Features and advantages of the present invention will be more clearly understood from the following detailed description of the accompanying drawings in which: FIG. 1 shows that when cleaning a Cu/Ti wiring substrate using the cleaning composition of the example crucible, Cu Figure 2 shows the surface of A1 when the m〇/a1/m〇 wiring substrate was cleaned using the cleaning composition of Example 2; Figure 3 shows the cleaning of Mo/Al/ when the cleaning composition of Comparative Example was used. The surface of A1 when the Mo wiring substrate is used; and FIG. 4 shows the surface of Cu when the wiring substrate is cleaned using the cleaning composition of Comparative Example 1. 15/19 201144429 [Explanation of main component symbols] None 16/19